EP3331964B1 - High temperature fracturing fluids with nanoparticles - Google Patents
High temperature fracturing fluids with nanoparticles Download PDFInfo
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- EP3331964B1 EP3331964B1 EP16745354.7A EP16745354A EP3331964B1 EP 3331964 B1 EP3331964 B1 EP 3331964B1 EP 16745354 A EP16745354 A EP 16745354A EP 3331964 B1 EP3331964 B1 EP 3331964B1
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- EP
- European Patent Office
- Prior art keywords
- fracturing fluid
- metal oxide
- per thousand
- litres
- polyacrylamide
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- 239000012530 fluid Substances 0.000 title claims description 103
- 239000002105 nanoparticle Substances 0.000 title claims description 82
- 239000004971 Cross linker Substances 0.000 claims description 72
- 229920002401 polyacrylamide Polymers 0.000 claims description 36
- 239000006185 dispersion Substances 0.000 claims description 34
- 229910044991 metal oxide Inorganic materials 0.000 claims description 34
- 150000004706 metal oxides Chemical class 0.000 claims description 33
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 26
- 229920001059 synthetic polymer Polymers 0.000 claims description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 20
- 229920000642 polymer Polymers 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 10
- 229910052726 zirconium Inorganic materials 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 7
- 239000003381 stabilizer Substances 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229920001897 terpolymer Polymers 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- 239000000872 buffer Substances 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 239000002280 amphoteric surfactant Substances 0.000 claims description 2
- 239000003945 anionic surfactant Substances 0.000 claims description 2
- 239000003139 biocide Substances 0.000 claims description 2
- 239000003093 cationic surfactant Substances 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 2
- 239000002888 zwitterionic surfactant Substances 0.000 claims description 2
- 238000013270 controlled release Methods 0.000 claims 1
- 239000002736 nonionic surfactant Substances 0.000 claims 1
- 229920006029 tetra-polymer Polymers 0.000 claims 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 79
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 21
- 239000000499 gel Substances 0.000 description 20
- XUXNAKZDHHEHPC-UHFFFAOYSA-M sodium bromate Chemical compound [Na+].[O-]Br(=O)=O XUXNAKZDHHEHPC-UHFFFAOYSA-M 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000005755 formation reaction Methods 0.000 description 8
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 6
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- -1 acrylates Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 5
- 239000008399 tap water Substances 0.000 description 5
- 235000020679 tap water Nutrition 0.000 description 5
- 244000007835 Cyamopsis tetragonoloba Species 0.000 description 4
- 239000008351 acetate buffer Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013068 control sample Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- XWNSFEAWWGGSKJ-UHFFFAOYSA-N 4-acetyl-4-methylheptanedinitrile Chemical compound N#CCCC(C)(C(=O)C)CCC#N XWNSFEAWWGGSKJ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000004153 Potassium bromate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- YRVUCYWJQFRCOB-UHFFFAOYSA-N n-butylprop-2-enamide Chemical compound CCCCNC(=O)C=C YRVUCYWJQFRCOB-UHFFFAOYSA-N 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- WDFKEEALECCKTJ-UHFFFAOYSA-N n-propylprop-2-enamide Chemical compound CCCNC(=O)C=C WDFKEEALECCKTJ-UHFFFAOYSA-N 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 235000019396 potassium bromate Nutrition 0.000 description 1
- 229940094037 potassium bromate Drugs 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 238000004457 water analysis Methods 0.000 description 1
- 239000003180 well treatment fluid Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/887—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/66—Compositions based on water or polar solvents
- C09K8/68—Compositions based on water or polar solvents containing organic compounds
- C09K8/685—Compositions based on water or polar solvents containing organic compounds containing cross-linking agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/882—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/885—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/10—Nanoparticle-containing well treatment fluids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/24—Bacteria or enzyme containing gel breakers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/26—Gel breakers other than bacteria or enzymes
Definitions
- Embodiments of the present disclosure generally relate to fracturing fluids, and more specifically relate to fracturing fluids comprising metal oxide nanoparticles.
- Thermally stable synthetic polymers such as polyacrylamide
- these polymers may be used in fracturing fluids at temperatures of 149 to 204 °C (300 to 400 °F); however, these polymers have to be employed at very high concentrations in order to generate enough viscosity to suspend proppant.
- the high polymer concentrations of these fluids make it very difficult to completely degrade at the end of a fracturing operation. Thus, polymer residue within the gas reservoir can block gas flow.
- WO 2012/122505 discloses a method of forming a wellbore fluid including introducing a hydratable polymer and introducing a crosslinker comprised of at least a silica material, wherein the crosslinker has a dimension of about 5-100 nm.
- EP 2848666 discloses well treatment fluids comprising nanoparticles
- WO 2013/052359 discloses a foam formed from a dispersion comprising nanoparticles and a gaseous reactant for recovery of hydrocarbons from a subterranean reservoir.
- a high temperature fracturing fluid comprising an aqueous fluid, carboxyl-containing synthetic polymers, metal oxide nanoparticles having a particle size of 0.1 to 500 nanometers; and a metal crosslinker which crosslinks the carboxyl-containing synthetic polymers and the metal oxide nanoparticles to form a crosslinked gel.
- the metal crosslinker is selected from the group consisting of zirconium crosslinkers, titanium crosslinkers, aluminum crosslinkers, chromium crosslinkers, iron crosslinkers, hafnium crosslinkers, antimony cross linkers, and combinations thereof.
- the metal oxide nanoparticles which may include transition metal oxides or rare earth oxides, increase the viscosity of the fracturing fluid, thereby allowing for a reduction in the concentration of polyacrylamide in the fracturing fluid.
- the fracturing fluid leaves less polymer residue, while maintaining its requisite viscosity at high temperatures, for example, 149 to 204 °C (300 to 400 °F).
- the present invention relates to a fracturing fluid according to claim 1, wherein the fracturing fluid is suitable to be injected down a wellbore at a rate and applied pressure sufficient for the fracturing fluid to flow into a subterranean formation and to initiate or extend fractures in the formation.
- the fracturing fluid comprises an aqueous fluid, a carboxyl-containing synthetic polymer, a metal crosslinker, and metal oxide nanoparticles.
- the metal crosslinker is selected from the group consisting of zirconium crosslinkers, titanium crosslinkers, aluminum crosslinkers, chromium crosslinkers, iron crosslinkers, hafnium crosslinkers, antimony cross linkers, and combinations thereof.
- the metal oxide nanoparticles interact with at least a portion of carboxyl-containing synthetic polymer (also called a base fluid) to exhibit an improved stability and viscosity.
- the metal oxide nanoparticles when used in fracturing fluids, increase the viscosity to allow better suspension of the proppant in the fracturing fluid. Proper suspension of the proppant holds the subterranean formation open to allow extraction of the gas or oil without any damage to the subterranean formation.
- nanoparticles means particles having an average particle size of 0.1 to 500 nanometers (nm). In one or more embodiments, the nanoparticles may have an average particle size of 1 to 100 nm, or 1 to 80 nm, or 5 to 75 nm, or 10 to 60 nm.
- the metal oxide of the metal oxide nanoparticles is selected from the group consisting of zirconium oxide, cerium oxide, titanium oxide and combinations thereof.
- the metal oxide nanoparticles may be added to the fracturing fluid in various forms, such as in powder form or in a dispersion, for example, an aqueous dispersion. As illustrated in Example 10 as follows, it is desirable in some embodiments to add the metal oxide nanoparticles in a dispersion, because it increases crosslinking with the carboxyl-containing synthetic polymer.
- the metal oxide nanoparticles may be stabilized with a polymer, a surfactant, or a combination thereof.
- the metal oxide nanoparticles may be stabilized with a polymer, such as polyvinylpyrrolidone.
- carboxyl-containing synthetic polymers are contemplated for the fracturing fluid.
- the carboxyl-containing synthetic polymer includes polymers produced from one or more monomers containing carboxyl groups or derivatives thereof, such as salts or esters of the carboxyl containing monomers (e.g., acrylates).
- the carboxyl-containing synthetic polymer may be a polyacrylamide polymer.
- the polyacrylamide polymer and copolymer may comprise a polyacrylamide copolymer, a polyacrylamide terpolymer, or combinations thereof.
- the polyacrylamide polymer, whether a copolymer, or terpolymer, may include at least one monomer selected from the group consisting of acrylic acid, or other monomers containing carboxyl groups or their salts or esters such as acrylates, and combinations thereof.
- acrylates examples include methyl acrylate, ethyl acrylate, n -propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert- butyl acrylate, n -octyl acrylate, and the like.
- Other monomers besides the carboxyl-containing monomer may include acrylamide, methacrylamide, N-substituted acrylamides.
- N-substituted acrylamides include, among others, N-methyl acrylamide, N-propyl acrylamide, N-butyl acrylamide, N,N-dimethyl acrylamide, N-methyl-N-sec-butyl acrylamide.
- the carboxyl-containing synthetic polymer may be a partially hydrolyzed carboxyl-containing synthetic polymer.
- the fracturing fluid also comprises a metal crosslinker which promotes crosslinking between the carboxyl-containing synthetic polymer to form three-dimensional polymer networks.
- the metal oxide nanoparticles are dispersed within this three dimension polymer network.
- the metal crosslinker is selected from the group consisting of zirconium crosslinkers, titanium crosslinkers, aluminum crosslinkers, chromium crosslinkers, iron crosslinkers, hafnium crosslinkers, antimony cross linkers, and combinations thereof.
- the metal crosslinkers may include organic metal oxide complexes.
- the metal crosslinker is a zirconium crosslinker.
- zirconium crosslinkers may include a zirconium alkanolamine complex, a zirconium alkanolamine polyol complex.
- Suitable commercial embodiments of the zirconium crosslinker may include TYZOR® 212 produced by Dorf Ketal Specialty Catalysts LLC.
- the metal crosslinker crosslinks the carboxyl-containing synthetic polymers to form a crosslinked gel.
- the fracturing fluid may comprise 0.12 to 12 kg per thousand litres (1 to 100 pounds per thousand gallons) (pptg) of crosslinked gel, or 1.8 to 6 kg per thousand litres (15 to 50 pptg) of crosslinked gel, or 2.4 to 5.4 kg per thousand litres (20 to 45 pptg) of crosslinked gel.
- the fracturing fluid may include 0.12 to 7.2 kg per thousand litres (1 to 60 pptg) of the carboxyl-containing synthetic polymer (e.g., polyacrylamide), or from 0.12 to 6 kg per thousand litres (1 to 50 pptg) of the carboxyl-containing synthetic polymer, or 1.2 to 6 kg per thousand litres (10 from 50 pptg) of the carboxyl-containing synthetic polymer, or from 2.4 to 4.8 kg per thousand litres (20 to 40 pptg) of the carboxyl-containing synthetic polymer.
- the presence of the metal oxide nanoparticles enables reduction of the carboxyl-containing synthetic polymer by amounts of 5% to 50 % by weight.
- the fracturing fluid may comprise from 0.0002% to about 2% by weight of the metal oxide nanoparticles, or from 0.002% to 0.5% by weight of metal oxide nanoparticles, or from 0.005% to 0.2% by weight of metal oxide nanoparticles. Additionally, the fracturing fluid includes from about 0.02% to about 2% by weight of the metal crosslinker.
- the fracturing fluid also includes additional additives, for example, additives that alter the salt concentration of the crosslinked gel.
- additional additives for example, additives that alter the salt concentration of the crosslinked gel.
- brine solution may be added, such as KCl or CaCl 2 .
- the fracturing fluid may also include additional components such as buffers, antioxidants, biocides, clay stabilizers, diverting agents, fluid loss additives, friction reducers, iron controllers, gel stabilizers, etc.
- the fracturing fluid may further comprise a surfactant, which may be used to lower the surface tension of the fracturing fluid.
- surfactants are contemplated, for example, anionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants, or combinations thereof.
- the fracturing fluid may also comprise a breaker to degrade the crosslinked gel.
- the breaker is used to "break" or reduce the viscosity of the fracturing fluid so that the fracturing fluid may be easily recovered from the fracture during clean up.
- the breaker may be an acid, an oxidizer, an enzyme breaker, a chelating agent, or a combination thereof. Examples of breakers include, but are not be limited to sodium bromate, potassium bromate, sodium persulfate, ammonium persulfate, potassium persulfate, and various peroxides.
- an encapsulant may be used to control or delay the release of the breaker encapsulated or disposed therein.
- the breaker may include a combination of encapsulated and unencapsulated breaker.
- the breaker may include a combination of sodium bromate and encapsulated sodium bromate.
- Table 1 as follows lists the components of the fracturing fluids used in the following Examples 1-10.
- Table 1 Product Name/Identifier Composition/Properties Supplier CELB-217-063-2 Partially hydrolyzed polyacrylamide terpolymer (80% active) ChemEOR CELB-225-010-2 Gel stabilizer/ antioxidant ChemEOR DP/EM 5015 Partially hydrolyzed polyacrylamide terpolymer (30% active) SNF TYZOR 212 Zr-based crosslinker (Type 2) Dorf Ketal Specialty Catalysts LLC ZrO 2 nanoparticles dispersion 45-55 nm; 20 wt% active in water U.S.
- Research Nanomaterials, Inc TiO 2 nanoparticles dispersion Rutile structure; 5-15 nm; 15 U.S. Research Nanomaterials, wt% active in water Inc CeO 2 nanoparticles dispersion 30-50 nm; 20 wt% active in water U.S. Research Nanomaterials, Inc Tetramethyl ammonium chloride (TMAC) dispersion Clay stabilizer (50 wt % active) PABA-152L Acetic acid/acetate buffer Precision Additives ProCap BR Encapsulated sodium bromate breaker Fritz Industries
- the crosslinked gel samples of Examples 1-6 were prepared using a Waring® blender. Referring to Table 1, polyacrylamide-based polymer, (for example, CELB-217-063-2, or DP/EM 5015), which is being used as the base fluid, was hydrated in tap water. Additional additives such as buffers, and antioxidant (CELB-225-010-2) may be added to the base fluid followed by the addition of metal oxide nanoparticles (ZrO 2 , TiO 2, and CeO 2 ) and the Zr-based metal crosslinker (Type 1, containing 5.8 wt.% ZrO 2 ).
- the samples of Examples 1-6 were generally prepared in a volume of 100 mL. A 52 mL fluid sample was placed into a Grace M5600 HPHT Rheometer equipped with a B5 Bob configuration. Tests were performed using a shear-rate of 40 s -1 at the temperature profiles depicted in FIGS. 1-6 respectively.
- a viscosity comparison was performed for: 1) a fracturing fluid comprising 3.6 kg per thousand litres (30 pptg) polyacrylamide (CELB-217-063-2), 5 litres per thousand litres (5 gpt) Zr-based crosslinker (Type 1, containing 5.8 wt.% ZrO 2 ), and a 1 litre per thousand litres (1.0 gpt) ZrO 2 nanoparticle dispersion; 2) a fracturing fluid comprising 3.6 kg per thousand litres (30 pptg) polyacrylamide (CELB-217-063-2) and 5 litres per thousand litres (5 gpt) Zr-based crosslinker (Type 1, containing 5.8 wt.% ZrO 2 ), but no ZrO 2 nanoparticle dispersion; and 3) a fracturing fluid comprising 3.6 kg per thousand litres (30 pptg) polyacrylamide (CELB-217-063-2), and a
- the viscosity curves of FIG. 1 demonstrate that the combination of the Zr-based crosslinker and the ZrO 2 nanoparticle dispersion achieves better viscosity stability than when the polyacrylamide is crosslinked with 5 litres per thousand litres (5 gpt) traditional Zr-based crosslinker (Type 1) alone. Without being bound by theory, the interaction between the ZrO 2 nanoparticles and partially hydrolyzed polyacrylamide reinforces the crosslinked gel and provides improved viscosity stability for the crosslinked gel.
- a fracturing fluid comprising 3 kg per thousand litres (25 pptg) polyacrylamide (CELB-217-063-2), 5 litres per thousand litres (5 gpt) Zr-based crosslinker (Type 1, containing 5.8 wt.% ZrO 2 ), and 1 litre per thousand litres (1.0 gpt) ZrO 2 nanoparticle dispersion (45-55 nm; 20 wt% active); and 2) a fracturing fluid comprising 3.6 kg per thousand litres (30 pptg) polyacrylamide (CELB-217-063-2) and 5 litres per thousand litres (5 gpt) Zr-based crosslinker (Type 1, containing 5.8 wt.% ZrO 2 ), but no ZrO 2 nanoparticles.
- the addition of the ZrO 2 metal oxide nanoparticles enables reduction of the polymer loading by 0.6 kg per thousand
- a viscosity comparison was performed at 149 °C (300 °F) for various fracturing fluids comprising 3.6 kg per thousand litres (30 pptg) polyacrylamide (DP/EM 5015) crosslinked with 5 litres per thousand litres (5 gpt) Zr-bascd crosslinker and ZrO 2 nanoparticle dispersion (45-55 nm; 20 wt% active) at multiple concentrations.
- three samples with the following amounts of ZrO 2 nanoparticles were tested: 1 litre per thousand litres, 2 litres per thousand litres and 3 litres per thousand litres (1.0 gpt, 2.0 gpt and 3.0 gpt, respectively).
- a viscosity comparison was performed at 149 °C (300 °F) for various fracturing fluids comprising 3.6 kg per thousand litres (30 pptg) polyacrylamide (DP/EM 5015) crosslinked with 0.6 kg per thousand litres (5 pptg) Zr-based crosslinker (Type 1) and a TiO 2 nanoparticle dispersion (Rutile; 5-15 nm; 15 wt% active in a dispersion form) at multiple concentrations.
- fracturing fluids comprising 3.6 kg per thousand litres (30 pptg) polyacrylamide (DP/EM 5015) crosslinked with 0.6 kg per thousand litres (5 pptg) Zr-based crosslinker (Type 1) and a TiO 2 nanoparticle dispersion (Rutile; 5-15 nm; 15 wt% active in a dispersion form) at multiple concentrations.
- a viscosity comparison was performed at 149 °C (300 °F) for various fracturing fluids comprising 3.6 kg per thousand litres (30 pptg) polyacrylamide (DP/EM 5015) crosslinked with 0.6 kg per thousand litres (5 pptg) Zr-based crosslinker (Type 1) and CeO 2 nanoparticle dispersion (30-50 nm; 20 wt% active in a dispersion form) at multiple concentrations.
- fracturing fluids comprising 3.6 kg per thousand litres (30 pptg) polyacrylamide (DP/EM 5015) crosslinked with 0.6 kg per thousand litres (5 pptg) Zr-based crosslinker (Type 1) and CeO 2 nanoparticle dispersion (30-50 nm; 20 wt% active in a dispersion form) at multiple concentrations.
- an oxidizer type breaker fluid was added separately after the fracturing process to eliminate the polymer residue from the fracture.
- a viscosity comparison was performed at 149 °C (300 °F) for various fracturing fluids having various concentrations of sodium bromate as a breaker.
- Each crosslinked gel sample included 3.6 kg per thousand litres (30 pptg) polyacrylamide (DP/EM 5015), 0.6 kg per thousand litres (5 pptg) Zr-based crosslinker (Type 1), and 2 litres per thousand litres (2.0 gpt) ZrO 2 nanoparticle dispersion; however, the samples differ in including the following amounts of sodium bromate breaker: zero breaker; 0.06 kg per thousand litres (0.5 pptg) sodium bromate; 0.12 kg per thousand litres (1.0 pptg) sodium bromate; and 0.24 kg per thousand litres (2.0 pptg) sodium bromate. As shown, the lowest concentration sodium bromate sample, 0.06 kg per thousand litres (0.5 pptg), was sufficient to break the crosslinked fracturing fluid.
- the samples of Examples 7-9 were formulated in accordance with the following procedure.
- the water analysis for this field water is in Table 2 as follows.
- the crosslinked gel includes 3.6 kg per thousand litres (30 pptg) polyacrylamide (DP/EM 5015), which was prepared by hydrating 12 grams of DP/EM 5015 in 1 liter of water at 1000 rpm for 30 min.
- Two water sources have been tested in this strategy, Houston tap water or synthetic field water from one of the Saudi Aramco wells as listed in Table 2.
- Fluid samples were prepared using a Waring® blender.
- the fracturing fluid was prepared by taking 100 mL of base fluid, followed by addition of pH adjusting agent, gel stabilizers, nanomaterials, and then Zr-based crosslinker (Type 2).
- Table 2 the analyzed field water source from Saudi Arabia had total dissolved solids (TDS) amount of about 850 ppm.
- Table 2 Ion Concentration (mg/L) Sulfate 126 Cl 461 HCO 3 - 231 CO 3 2- 12 Ca 0.6 Mg 1.1 Fe 3.22
- FIG. 7 depicts the effect on viscosity at a temperature of 149 °C (300 °F) when using the combination of an unencapsulated breaker and an encapsulated breaker.
- the breaker containing fracturing fluid and the comparative breaker-free fracturing fluid comprises 3.6 kg per thousand litres (30 pptg) DP/EM 5015 (hydrated in Synthetic field water), 1.8 litres per thousand litres (1.8 gpt) 20% acetic acid, 1 litre per thousand litres (1.0 gpt) CELB-225-010-2, 2 litres per thousand litres (2.0 gpt) TMAC, 1.0 gpt ZrO 2 nanoparticle solution, and 0.5 litre per thousand litres (0.5 gpt) Zr-based crosslinker (Type 2).
- the pH of the fluid is about 5.3.
- the breaker containing fluid includes 0.03 kg per thousand litres (0.25 pptg) sodium bromate and 0.24 kg per thousand litres (2 pptg) ProCap BR. As shown, when no breaker is utilized, there is still some viscosity remaining, which correlates with polyacrylamide residue buildup.
- FIG. 8 depicts the effect on viscosity at a temperature of 177 °C (350 °F) when using an encapsulated breaker.
- the breaker containing fracturing fluid and the comparative breaker-free fracturing fluid includes 3.6 kg per thousand litres (30 pptg) DP/EM 5015, 1.8 litres per thousand litres (1.8 gpt) 20% acetic acid, 2 litres per thousand litres (2.0 gpt) CELB-225-010-2, 2 litres per thousand litres (2.0 gpt) 50% TMAC, 1 litre per thousand litres (1.0 gpt) ZrO 2 nanoparticle solution, and 0.9 litre per thousand litres (0.9 gpt) Zr-based crosslinker (Type 2) (pH ⁇ 5.4).
- the breaker containing fracturing fluid included 0.47 kg per thousand litres (3.9 pptg) ProCap BR encapsulated breaker. Similar to Example 7, when no breaker is utilized as shown in FIG. 8 , there is still some viscosity remaining, whereas the breaker reduces the viscosity to essentially zero
- FIG. 9 depicts the stabilizing effect on viscosity at a temperature of 204 °C (400 °F) when using ZrO 2 nanoparticles.
- the fracturing fluid which includes 3.6 kg per thousand litres (30 pptg) DP/EM 5015 (hydrated in Synthetic field water), 1.8 litres per thousand litres (1.8 gpt) 20% acetic acid, 3 litres per thousand litres (3.0 gpt) CELB-225-010-2, 2 litres per thousand litres (2.0 gpt) 50% TMAC, 1 litre per thousand litres (1.0 gpt) ZrO 2 nanoparticle solution, and 0.9 litre per thousand litres (0.9 gpt) Zr-based crosslinker (Type 2) (pH ⁇ 5.4), maintains a viscosity above 500 cP at a shear rate of 40 s -1 for about 75 min.
- fracturing fluid samples comprise the following component mixtures:
- No nanomaterials 100 mL 25# DP/EM 5015 in Tap Water, 0.37 mL PABA-152L (acetic acid/acetate buffer), 0.05 mL CELB 225-010-2, 0.2 mL 50% TMAC, and 0.06 mL Zr-based crosslinker (Type 2).
- the fluid mixture has a final pH of approximately 5.12.
- ZrO 2 nanodispersion 100 mL 25# DP/EM 5015 in Tap Water, 0.1 mL ZrO 2 nanoparticles (45-55 nm; 20% dispersion; contains 20 mg of nanoparticles), 0.37 mL PABA-152L (acetic acid/acetate buffer), 0.05 mL CELB 225-010-2, 0.2 mL 50% TMAC, and 0.06 mL Zr-based crosslinker (Type 2).
- the fluid mixture has a final pH of approximately 5.30.
- ZrO 2 powder 100 mL 25# DP/EM 5015 in Tap Water, 40 mg ZrO 2 nanoparticles (powder; high purity, 99.95%), 0.37 mL PABA-152L (acetic acid/acetate buffer), 0.05 mL CELB 225-010-2, 0.2 mL 50% TMAC, and 0.06 mL Zr-based crosslinker (Type 2).
- the fluid mixture has a final pH of approximately 5.32.
- the addition of 20 mg of ZrO 2 nanoparticles in dispersion form maintains the viscosity above 500 cP at a shear rate of 40 s -1 for 130 mins, which is a 50% increase compared to the fluid without nanoparticles. Moreover, even with addition of double amount of the ZrO 2 nanoparticle powder, the viscosity improvement (500 cp at 40 s -1 for 99 min) is less than the viscosity improvement achieved by the samples with 20 mg of ZrO 2 nanoparticles in a dispersion form.
Description
- Embodiments of the present disclosure generally relate to fracturing fluids, and more specifically relate to fracturing fluids comprising metal oxide nanoparticles.
- Considerable attention has been devoted to extracting the gas locked within tight subterranean gas formations with permeability in the nano-darcy to micro-darcy range; however, these tight subterranean gas formations are characterized by high temperatures and high pressures. For example, these formations are subject to temperatures around 149 to 204 °C (300 to 400 °F). Traditional hydraulic fracturing fluids may utilize crosslinked polysaccharide gels, such as guar and guar derivatives, to transport proppant from the surface to the desired treatment zone; however, the guar and guar derivatives are unstable at these higher temperatures.
- Thermally stable synthetic polymers, such as polyacrylamide, may be used in fracturing fluids at temperatures of 149 to 204 °C (300 to 400 °F); however, these polymers have to be employed at very high concentrations in order to generate enough viscosity to suspend proppant. The high polymer concentrations of these fluids make it very difficult to completely degrade at the end of a fracturing operation. Thus, polymer residue within the gas reservoir can block gas flow.
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WO 2012/122505 discloses a method of forming a wellbore fluid including introducing a hydratable polymer and introducing a crosslinker comprised of at least a silica material, wherein the crosslinker has a dimension of about 5-100 nm.EP 2848666 discloses well treatment fluids comprising nanoparticles, andWO 2013/052359 discloses a foam formed from a dispersion comprising nanoparticles and a gaseous reactant for recovery of hydrocarbons from a subterranean reservoir. - Accordingly, ongoing needs exist for fracturing fluids that are stable at high temperatures, while reducing polymer residue within subterranean gas formations.
- The embodiments of the present disclosure meet these needs by utilizing a high temperature fracturing fluid comprising an aqueous fluid, carboxyl-containing synthetic polymers, metal oxide nanoparticles having a particle size of 0.1 to 500 nanometers; and a metal crosslinker which crosslinks the carboxyl-containing synthetic polymers and the metal oxide nanoparticles to form a crosslinked gel. The metal crosslinker is selected from the group consisting of zirconium crosslinkers, titanium crosslinkers, aluminum crosslinkers, chromium crosslinkers, iron crosslinkers, hafnium crosslinkers, antimony cross linkers, and combinations thereof.
- The metal oxide nanoparticles, which may include transition metal oxides or rare earth oxides, increase the viscosity of the fracturing fluid, thereby allowing for a reduction in the concentration of polyacrylamide in the fracturing fluid. By reducing the concentration of polyacrylamide in the fracturing fluid, the fracturing fluid leaves less polymer residue, while maintaining its requisite viscosity at high temperatures, for example, 149 to 204 °C (300 to 400 °F).
- Additional features and advantages of the described embodiments will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from that description or recognized by practicing the described embodiments, including the detailed description which follows, the claims, as well as the appended drawings.
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FIG. 1 is a graph of viscosity versus time and temperature for: 1) a fracturing fluid comprising polyacrylamide, Zr-based crosslinker (Type 1), and ZrO2 nanoparticle dispersion; 2) a fracturing fluid comprising polyacrylamide and a Zr-based crosslinker (Type 1), but no ZrO2 nanoparticle dispersion; and 3) ZrO2 nanoparticle dispersion, according to one or more embodiments of the present disclosure. -
FIG. 2 is another graph of viscosity versus time and temperature for: 1) a fracturing fluid comprising polyacrylamide, Zr-based crosslinker (Type 1), and ZrO2 nanoparticle dispersion; and 2) a fracturing fluid comprising polyacrylamide and a Zr-based crosslinker (Type 1), but no ZrO2 nanoparticle dispersion, according to one or more embodiments of the present disclosure. -
FIG. 3 is a graph of viscosity versus time and temperature comparing fracturing fluids with varying amounts of ZrO2 nanoparticle dispersions, according to one or more embodiments of the present disclosure. -
FIG. 4 is a graph of viscosity versus time and temperature comparing fracturing fluids with varying amounts of TiO2 nanoparticle dispersions, according to one or more embodiments of the present disclosure. -
FIG. 5 is a graph of viscosity versus time and temperature comparing fracturing fluids with varying amounts of CeO2 nanoparticle dispersions, according to one or more embodiments of the present disclosure. -
FIG. 6 is a graph of viscosity versus time and temperature comparing fracturing fluids with varying amounts of sodium bromate breaker added, according to one or more embodiments of the present disclosure. -
FIG. 7 is a graph of viscosity versus time and temperature comparing a fracturing fluid comprising a combination of encapsulated breaker and unencapsulated sodium bromate breaker versus a fracturing fluid without breaker added, according to one or more embodiments of the present disclosure. -
FIG. 8 is a graph of viscosity versus time and temperature comparing fracturing fluids with and without sodium bromate breaker added, according to one or more embodiments of the present disclosure. -
FIG. 9 is a graph of viscosity versus time and temperature for a sample fracturing fluid with ZrO2 nanoparticle dispersion, according to one or more embodiments of the present disclosure. -
FIG. 10 is a graph of viscosity versus time and temperature comparing fracturing fluids with nanoparticles in powder form or dispersion form, according to one or more embodiments of the present disclosure. - The embodiments set forth in the drawings are illustrative in nature and not intended to be limiting to the claims. Moreover, individual features of the drawings will be more fully apparent and understood in view of the detailed description.
- The present invention relates to a fracturing fluid according to
claim 1, wherein the fracturing fluid is suitable to be injected down a wellbore at a rate and applied pressure sufficient for the fracturing fluid to flow into a subterranean formation and to initiate or extend fractures in the formation. - In one or more embodiments, the fracturing fluid comprises an aqueous fluid, a carboxyl-containing synthetic polymer, a metal crosslinker, and metal oxide nanoparticles. The metal crosslinker is selected from the group consisting of zirconium crosslinkers, titanium crosslinkers, aluminum crosslinkers, chromium crosslinkers, iron crosslinkers, hafnium crosslinkers, antimony cross linkers, and combinations thereof. The metal oxide nanoparticles interact with at least a portion of carboxyl-containing synthetic polymer (also called a base fluid) to exhibit an improved stability and viscosity. The metal oxide nanoparticles, when used in fracturing fluids, increase the viscosity to allow better suspension of the proppant in the fracturing fluid. Proper suspension of the proppant holds the subterranean formation open to allow extraction of the gas or oil without any damage to the subterranean formation.
- As used herein, "nanoparticles" means particles having an average particle size of 0.1 to 500 nanometers (nm). In one or more embodiments, the nanoparticles may have an average particle size of 1 to 100 nm, or 1 to 80 nm, or 5 to 75 nm, or 10 to 60 nm.
- Various metal oxide nanoparticles are contemplated. The metal oxide of the metal oxide nanoparticles is selected from the group consisting of zirconium oxide, cerium oxide, titanium oxide and combinations thereof. The metal oxide nanoparticles may be added to the fracturing fluid in various forms, such as in powder form or in a dispersion, for example, an aqueous dispersion. As illustrated in Example 10 as follows, it is desirable in some embodiments to add the metal oxide nanoparticles in a dispersion, because it increases crosslinking with the carboxyl-containing synthetic polymer. Moreover, in further embodiments, the metal oxide nanoparticles may be stabilized with a polymer, a surfactant, or a combination thereof. In a specific embodiment, the metal oxide nanoparticles may be stabilized with a polymer, such as polyvinylpyrrolidone.
- Similarly, various carboxyl-containing synthetic polymers are contemplated for the fracturing fluid. As used herein, the carboxyl-containing synthetic polymer includes polymers produced from one or more monomers containing carboxyl groups or derivatives thereof, such as salts or esters of the carboxyl containing monomers (e.g., acrylates).
- For example, the carboxyl-containing synthetic polymer may be a polyacrylamide polymer. In one or more embodiments, the polyacrylamide polymer and copolymer may comprise a polyacrylamide copolymer, a polyacrylamide terpolymer, or combinations thereof. The polyacrylamide polymer, whether a copolymer, or terpolymer, may include at least one monomer selected from the group consisting of acrylic acid, or other monomers containing carboxyl groups or their salts or esters such as acrylates, and combinations thereof. Examples of said acrylates include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-octyl acrylate, and the like. Other monomers besides the carboxyl-containing monomer may include acrylamide, methacrylamide, N-substituted acrylamides. Further examples of said N-substituted acrylamides include, among others, N-methyl acrylamide, N-propyl acrylamide, N-butyl acrylamide, N,N-dimethyl acrylamide, N-methyl-N-sec-butyl acrylamide. In other embodiments, the carboxyl-containing synthetic polymer may be a partially hydrolyzed carboxyl-containing synthetic polymer. The Examples which follow depict one of many possible suitable examples, a partially hydrolyzed polyacrylamide terpolymer. Various percentages of hydrolysis are contemplated as would be familiar to the skilled person.
- As stated above, the fracturing fluid also comprises a metal crosslinker which promotes crosslinking between the carboxyl-containing synthetic polymer to form three-dimensional polymer networks. The metal oxide nanoparticles are dispersed within this three dimension polymer network. The metal crosslinker is selected from the group consisting of zirconium crosslinkers, titanium crosslinkers, aluminum crosslinkers, chromium crosslinkers, iron crosslinkers, hafnium crosslinkers, antimony cross linkers, and combinations thereof. The metal crosslinkers may include organic metal oxide complexes.
- In one embodiment, the metal crosslinker is a zirconium crosslinker. Examples of zirconium crosslinkers may include a zirconium alkanolamine complex, a zirconium alkanolamine polyol complex. Suitable commercial embodiments of the zirconium crosslinker may include TYZOR® 212 produced by Dorf Ketal Specialty Catalysts LLC.
- As stated previously, the metal crosslinker crosslinks the carboxyl-containing synthetic polymers to form a crosslinked gel. Various amounts are contemplated for the crosslinked gel. In one or more embodiments, the fracturing fluid may comprise 0.12 to 12 kg per thousand litres (1 to 100 pounds per thousand gallons) (pptg) of crosslinked gel, or 1.8 to 6 kg per thousand litres (15 to 50 pptg) of crosslinked gel, or 2.4 to 5.4 kg per thousand litres (20 to 45 pptg) of crosslinked gel.
- Additionally, various amounts are contemplated for the individual components of the fracturing fluid. For example and not by way of limitation, the fracturing fluid may include 0.12 to 7.2 kg per thousand litres (1 to 60 pptg) of the carboxyl-containing synthetic polymer (e.g., polyacrylamide), or from 0.12 to 6 kg per thousand litres (1 to 50 pptg) of the carboxyl-containing synthetic polymer, or 1.2 to 6 kg per thousand litres (10 from 50 pptg) of the carboxyl-containing synthetic polymer, or from 2.4 to 4.8 kg per thousand litres (20 to 40 pptg) of the carboxyl-containing synthetic polymer. As will be shown further in the Examples, the presence of the metal oxide nanoparticles enables reduction of the carboxyl-containing synthetic polymer by amounts of 5% to 50 % by weight.
- Moreover, in further embodiments, the fracturing fluid may comprise from 0.0002% to about 2% by weight of the metal oxide nanoparticles, or from 0.002% to 0.5% by weight of metal oxide nanoparticles, or from 0.005% to 0.2% by weight of metal oxide nanoparticles. Additionally, the fracturing fluid includes from about 0.02% to about 2% by weight of the metal crosslinker.
- The fracturing fluid also includes additional additives, for example, additives that alter the salt concentration of the crosslinked gel. In one or more embodiments, brine solution may be added, such as KCl or CaCl2.
- Optionally, the fracturing fluid may also include additional components such as buffers, antioxidants, biocides, clay stabilizers, diverting agents, fluid loss additives, friction reducers, iron controllers, gel stabilizers, etc. The fracturing fluid may further comprise a surfactant, which may be used to lower the surface tension of the fracturing fluid. Various surfactants are contemplated, for example, anionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants, or combinations thereof.
- Optionally, the fracturing fluid may also comprise a breaker to degrade the crosslinked gel. The breaker is used to "break" or reduce the viscosity of the fracturing fluid so that the fracturing fluid may be easily recovered from the fracture during clean up. In one or more embodiments, the breaker may be an acid, an oxidizer, an enzyme breaker, a chelating agent, or a combination thereof. Examples of breakers include, but are not be limited to sodium bromate, potassium bromate, sodium persulfate, ammonium persulfate, potassium persulfate, and various peroxides. Additionally, an encapsulant may be used to control or delay the release of the breaker encapsulated or disposed therein. In one or more embodiments, the breaker may include a combination of encapsulated and unencapsulated breaker. For example, the breaker may include a combination of sodium bromate and encapsulated sodium bromate.
- The various embodiments of the present disclosure will be further clarified by the following examples. The examples are illustrative in nature, and should not be understood to limit the subject matter of the present disclosure.
- Table 1 as follows lists the components of the fracturing fluids used in the following Examples 1-10.
Table 1 Product Name/Identifier Composition/Properties Supplier CELB-217-063-2 Partially hydrolyzed polyacrylamide terpolymer (80% active) ChemEOR CELB-225-010-2 Gel stabilizer/ antioxidant ChemEOR DP/EM 5015 Partially hydrolyzed polyacrylamide terpolymer (30% active) SNF TYZOR 212 Zr-based crosslinker (Type 2) Dorf Ketal Specialty Catalysts LLC ZrO2 nanoparticles dispersion 45-55 nm; 20 wt% active in water U.S. Research Nanomaterials, Inc TiO2 nanoparticles dispersion Rutile structure; 5-15 nm; 15 U.S. Research Nanomaterials, wt% active in water Inc CeO2 nanoparticles dispersion 30-50 nm; 20 wt% active in water U.S. Research Nanomaterials, Inc Tetramethyl ammonium chloride (TMAC) dispersion Clay stabilizer (50 wt % active) PABA-152L Acetic acid/acetate buffer Precision Additives ProCap BR Encapsulated sodium bromate breaker Fritz Industries - The crosslinked gel samples of Examples 1-6 were prepared using a Waring® blender. Referring to Table 1, polyacrylamide-based polymer, (for example, CELB-217-063-2, or DP/EM 5015), which is being used as the base fluid, was hydrated in tap water. Additional additives such as buffers, and antioxidant (CELB-225-010-2) may be added to the base fluid followed by the addition of metal oxide nanoparticles (ZrO2, TiO2, and CeO2) and the Zr-based metal crosslinker (
Type 1, containing 5.8 wt.% ZrO2). The samples of Examples 1-6 were generally prepared in a volume of 100 mL. A 52 mL fluid sample was placed into a Grace M5600 HPHT Rheometer equipped with a B5 Bob configuration. Tests were performed using a shear-rate of 40 s-1 at the temperature profiles depicted inFIGS. 1-6 respectively. - As shown in
FIG. 1 , a viscosity comparison was performed for: 1) a fracturing fluid comprising 3.6 kg per thousand litres (30 pptg) polyacrylamide (CELB-217-063-2), 5 litres per thousand litres (5 gpt) Zr-based crosslinker (Type 1, containing 5.8 wt.% ZrO2), and a 1 litre per thousand litres (1.0 gpt) ZrO2 nanoparticle dispersion; 2) a fracturing fluid comprising 3.6 kg per thousand litres (30 pptg) polyacrylamide (CELB-217-063-2) and 5 litres per thousand litres (5 gpt) Zr-based crosslinker (Type 1, containing 5.8 wt.% ZrO2), but no ZrO2 nanoparticle dispersion; and 3) a fracturing fluid comprising 3.6 kg per thousand litres (30 pptg) polyacrylamide (CELB-217-063-2), and a 1 litre per thousand litres (1.0 gpt) ZrO2 nanoparticle dispersion (45-55 nm; 20 wt% active), but no Zr-based crosslinker. The viscosity curves ofFIG. 1 demonstrate that the combination of the Zr-based crosslinker and the ZrO2 nanoparticle dispersion achieves better viscosity stability than when the polyacrylamide is crosslinked with 5 litres per thousand litres (5 gpt) traditional Zr-based crosslinker (Type 1) alone. Without being bound by theory, the interaction between the ZrO2 nanoparticles and partially hydrolyzed polyacrylamide reinforces the crosslinked gel and provides improved viscosity stability for the crosslinked gel. - As shown in
FIG. 2 , another viscosity comparison was performed for: 1) a fracturing fluid comprising 3 kg per thousand litres (25 pptg) polyacrylamide (CELB-217-063-2), 5 litres per thousand litres (5 gpt) Zr-based crosslinker (Type 1, containing 5.8 wt.% ZrO2), and 1 litre per thousand litres (1.0 gpt) ZrO2 nanoparticle dispersion (45-55 nm; 20 wt% active); and 2) a fracturing fluid comprising 3.6 kg per thousand litres (30 pptg) polyacrylamide (CELB-217-063-2) and 5 litres per thousand litres (5 gpt) Zr-based crosslinker (Type 1, containing 5.8 wt.% ZrO2), but no ZrO2 nanoparticles. As shown, the addition of the ZrO2 metal oxide nanoparticles enables reduction of the polymer loading by 0.6 kg per thousand litres (5 pptg) (a 17% loading reduction), while increasing and stabilizing the viscosity. - As shown in
FIG. 3 , a viscosity comparison was performed at 149 °C (300 °F) for various fracturing fluids comprising 3.6 kg per thousand litres (30 pptg) polyacrylamide (DP/EM 5015) crosslinked with 5 litres per thousand litres (5 gpt) Zr-bascd crosslinker and ZrO2 nanoparticle dispersion (45-55 nm; 20 wt% active) at multiple concentrations. Specifically, three samples with the following amounts of ZrO2 nanoparticles were tested: 1 litre per thousand litres, 2 litres per thousand litres and 3 litres per thousand litres (1.0 gpt, 2.0 gpt and 3.0 gpt, respectively). All three tests performed better than the control sample, which does not include ZrO2 nanoparticles, thereby indicating that the addition of metal oxide nanoparticles help in stabilizing the viscosity of the fracturing fluid at high temperatures. Surprisingly, the crosslinked gel with addition of 2 litres per thousand litres (2.0 gpt) of ZrO2 nanoparticles performed the best and remained above 800 cP at the shear rate of 40 s-1 for more than 180 min at 149 °C (300 °F). - As shown in
FIG. 4 , a viscosity comparison was performed at 149 °C (300 °F) for various fracturing fluids comprising 3.6 kg per thousand litres (30 pptg) polyacrylamide (DP/EM 5015) crosslinked with 0.6 kg per thousand litres (5 pptg) Zr-based crosslinker (Type 1) and a TiO2 nanoparticle dispersion (Rutile; 5-15 nm; 15 wt% active in a dispersion form) at multiple concentrations. Specifically, three samples with the following amounts of TiO2 nanoparticles were tested: 1 litre per thousand litres, 2 litres per thousand litres and 3 litres per thousand litres (1.0 gpt, 2.0 gpt and 3.0 gpt, respectively). Similar to the Example 3 samples with ZrO2 nanoparticles, all three samples with TiO2 nanoparticles performed better than the control sample, which does not include TiO2 nanoparticles. Surprisingly, the crosslinked gel with the addition of 1.0 gpt of TiO2 nanoparticles performed the best and remained above 650 cP at the shear rate of 40 s-1 for more than 180 min at 149 °C (300 °F). - As shown in
FIG. 5 , a viscosity comparison was performed at 149 °C (300 °F) for various fracturing fluids comprising 3.6 kg per thousand litres (30 pptg) polyacrylamide (DP/EM 5015) crosslinked with 0.6 kg per thousand litres (5 pptg) Zr-based crosslinker (Type 1) and CeO2 nanoparticle dispersion (30-50 nm; 20 wt% active in a dispersion form) at multiple concentrations. Specifically, three samples with the following amounts of CeO2 nanoparticles were tested: 1 litre per thousand litres, 2 litres per thousand litres and 3 litres per thousand litres (1.0 gpt, 2.0 gpt and 3.0 gpt, respectively). The crosslinked gel with the addition of 3 litres per thousand litres (3.0 gpt) of CeO2 nanoparticles performed the best and remained above 1250 cP at the shear rate of 40 s-1 for more than 150 min at 149 °C (300 °F). - As stated previously, an oxidizer type breaker fluid was added separately after the fracturing process to eliminate the polymer residue from the fracture. Referring to
FIG. 6 , a viscosity comparison was performed at 149 °C (300 °F) for various fracturing fluids having various concentrations of sodium bromate as a breaker. Each crosslinked gel sample included 3.6 kg per thousand litres (30 pptg) polyacrylamide (DP/EM 5015), 0.6 kg per thousand litres (5 pptg) Zr-based crosslinker (Type 1), and 2 litres per thousand litres (2.0 gpt) ZrO2 nanoparticle dispersion; however, the samples differ in including the following amounts of sodium bromate breaker: zero breaker; 0.06 kg per thousand litres (0.5 pptg) sodium bromate; 0.12 kg per thousand litres (1.0 pptg) sodium bromate; and 0.24 kg per thousand litres (2.0 pptg) sodium bromate. As shown, the lowest concentration sodium bromate sample, 0.06 kg per thousand litres (0.5 pptg), was sufficient to break the crosslinked fracturing fluid. - The samples of Examples 7-9 were formulated in accordance with the following procedure. The water analysis for this field water is in Table 2 as follows. The crosslinked gel includes 3.6 kg per thousand litres (30 pptg) polyacrylamide (DP/EM 5015), which was prepared by hydrating 12 grams of DP/EM 5015 in 1 liter of water at 1000 rpm for 30 min. Two water sources have been tested in this strategy, Houston tap water or synthetic field water from one of the Saudi Aramco wells as listed in Table 2. Fluid samples were prepared using a Waring® blender. The fracturing fluid was prepared by taking 100 mL of base fluid, followed by addition of pH adjusting agent, gel stabilizers, nanomaterials, and then Zr-based crosslinker (Type 2). In Table 2 below, the analyzed field water source from Saudi Arabia had total dissolved solids (TDS) amount of about 850 ppm.
Table 2 Ion Concentration (mg/L) Sulfate 126 Cl 461 HCO3 - 231 CO3 2- 12 Ca 0.6 Mg 1.1 Fe 3.22 -
FIG. 7 depicts the effect on viscosity at a temperature of 149 °C (300 °F) when using the combination of an unencapsulated breaker and an encapsulated breaker. As shown, the breaker containing fracturing fluid and the comparative breaker-free fracturing fluid comprises 3.6 kg per thousand litres (30 pptg) DP/EM 5015 (hydrated in Synthetic field water), 1.8 litres per thousand litres (1.8 gpt) 20% acetic acid, 1 litre per thousand litres (1.0 gpt) CELB-225-010-2, 2 litres per thousand litres (2.0 gpt) TMAC, 1.0 gpt ZrO2 nanoparticle solution, and 0.5 litre per thousand litres (0.5 gpt) Zr-based crosslinker (Type 2). The pH of the fluid is about 5.3. Additionally, the breaker containing fluid includes 0.03 kg per thousand litres (0.25 pptg) sodium bromate and 0.24 kg per thousand litres (2 pptg) ProCap BR. As shown, when no breaker is utilized, there is still some viscosity remaining, which correlates with polyacrylamide residue buildup. -
FIG. 8 depicts the effect on viscosity at a temperature of 177 °C (350 °F) when using an encapsulated breaker. As shown, the breaker containing fracturing fluid and the comparative breaker-free fracturing fluid includes 3.6 kg per thousand litres (30 pptg) DP/EM 5015, 1.8 litres per thousand litres (1.8 gpt) 20% acetic acid, 2 litres per thousand litres (2.0 gpt) CELB-225-010-2, 2 litres per thousand litres (2.0 gpt) 50% TMAC, 1 litre per thousand litres (1.0 gpt) ZrO2 nanoparticle solution, and 0.9 litre per thousand litres (0.9 gpt) Zr-based crosslinker (Type 2) (pH∼5.4). The breaker containing fracturing fluid included 0.47 kg per thousand litres (3.9 pptg) ProCap BR encapsulated breaker. Similar to Example 7, when no breaker is utilized as shown inFIG. 8 , there is still some viscosity remaining, whereas the breaker reduces the viscosity to essentially zero -
FIG. 9 depicts the stabilizing effect on viscosity at a temperature of 204 °C (400 °F) when using ZrO2 nanoparticles. As shown, the fracturing fluid, which includes 3.6 kg per thousand litres (30 pptg) DP/EM 5015 (hydrated in Synthetic field water), 1.8 litres per thousand litres (1.8 gpt) 20% acetic acid, 3 litres per thousand litres (3.0 gpt) CELB-225-010-2, 2 litres per thousand litres (2.0 gpt) 50% TMAC, 1 litre per thousand litres (1.0 gpt) ZrO2 nanoparticle solution, and 0.9 litre per thousand litres (0.9 gpt) Zr-based crosslinker (Type 2) (pH∼5.4), maintains a viscosity above 500 cP at a shear rate of 40 s-1 for about 75 min. - As shown in
FIG. 10 , a viscosity comparison was performed at 149 °C (300 °F) for fracturing fluids comprising ZrO2 nanoparticles in powder or dispersion form. The fracturing fluid samples comprise the following component mixtures: - No nanomaterials: 100 mL 25# DP/EM 5015 in Tap Water, 0.37 mL PABA-152L (acetic acid/acetate buffer), 0.05 mL CELB 225-010-2, 0.2
mL 50% TMAC, and 0.06 mL Zr-based crosslinker (Type 2). The fluid mixture has a final pH of approximately 5.12. - ZrO2 nanodispersion: 100 mL 25# DP/EM 5015 in Tap Water, 0.1 mL ZrO2 nanoparticles (45-55 nm; 20% dispersion; contains 20 mg of nanoparticles), 0.37 mL PABA-152L (acetic acid/acetate buffer), 0.05 mL CELB 225-010-2, 0.2
mL 50% TMAC, and 0.06 mL Zr-based crosslinker (Type 2). The fluid mixture has a final pH of approximately 5.30. - ZrO2 powder: 100 mL 25# DP/EM 5015 in Tap Water, 40 mg ZrO2 nanoparticles (powder; high purity, 99.95%), 0.37 mL PABA-152L (acetic acid/acetate buffer), 0.05 mL CELB 225-010-2, 0.2
mL 50% TMAC, and 0.06 mL Zr-based crosslinker (Type 2). The fluid mixture has a final pH of approximately 5.32. - Referring to
FIG. 10 , the addition of 20 mg of ZrO2 nanoparticles in dispersion form maintains the viscosity above 500 cP at a shear rate of 40 s-1 for 130 mins, which is a 50% increase compared to the fluid without nanoparticles. Moreover, even with addition of double amount of the ZrO2 nanoparticle powder, the viscosity improvement (500 cp at 40 s-1 for 99 min) is less than the viscosity improvement achieved by the samples with 20 mg of ZrO2 nanoparticles in a dispersion form.
Claims (13)
- A fracturing fluid comprising:an aqueous fluid;carboxyl-containing synthetic polymers,metal oxide nanoparticles having a particle size of 0.1 to 500 nanometers; anda metal crosslinker,wherein the metal crosslinker is selected from the group consisting of zirconium crosslinkers, titanium crosslinkers, aluminum crosslinkers, iron crosslinkers, hafnium crosslinkers, antimony cross linkers and combinations thereof,the metal crosslinker crosslinks the carboxyl-containing synthetic polymers to form a crosslinked gel,wherein the metal oxide nanoparticles are dispersed within the crosslinked gel and the metal oxide nanoparticles consist of metal oxide,wherein the metal oxide of the metal oxide nanoparticles is selected from the group consisting of zirconium oxide, cerium oxide, titanium oxide, and combinations thereof.
- The fracturing fluid of claim 1, wherein the carboxyl-containing synthetic polymers comprise an acrylamide-based polymer.
- The fracturing fluid of claim 2, wherein the acrylamide-based polymer comprises a polyacrylamide copolymer, a polyacrylamide terpolymer, a polyacrylamide tetrapolymer, or combinations thereof.
- The fracturing fluid of claim 3, wherein the polyacrylamide copolymer includes at least one monomer selected from the group consisting of acrylic acid, and acrylic acid derivatives.
- The fracturing fluid of claim 1, wherein the fracturing fluid comprises from 0.0002% to 2% by weight of metal oxide nanoparticles.
- The fracturing fluid of claim 1, wherein the fracturing fluid comprises from 0.02% to 2% by weight of metal crosslinker.
- The fracturing fluid of claim 1, wherein the fracturing fluid comprises from 0.12 to 7.2 kg per thousand litres (1 to 60 pptg) of carboxyl-containing synthetic polymer.
- The fracturing fluid of claim 1, wherein the fracturing fluid comprises one or more additives, wherein the additives are selected from the group consisting of buffers, antioxidants, biocides, clay stabilizers, diverting agents, fluid loss additives, friction reducers, iron controllers, gel stabilizers, anionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants, nonionic surfactants, and combinations thereof.
- The fracturing fluid of claim 1, wherein the fracturing fluid comprises 0.12 to 12 kg per thousand litres (1 to 100 pptg) of crosslinked gel.
- The fracturing fluid of claim 1, further comprising a viscosity breaker to degrade the crosslinked gel; preferably wherein the viscosity breaker is encapsulated for controlled release of the viscosity breaker.
- The fracturing fluid of claim 1, wherein the fracturing fluid comprises 0.12 to 12 kg per thousand litres (1 to 100 pptg) of crosslinked gel, wherein the carboxyl-containing synthetic polymer is a polyacrylamide and the crosslinked gel comprises 0.12 to 6 kg per thousand litres (1 to 50 pptg) of the polyacrylamide, and wherein the metal oxide nanoparticles are zirconium oxide nanoparticles, and the metal crosslinker is a zirconium crosslinker.
- The fracturing fluid of claim 1, wherein the metal oxide nanoparticles comprise transition metal oxides, rare earth metal oxides or combinations thereof.
- The fracturing fluid of claim 1, wherein the metal oxide nanoparticles are in a metal oxide nanoparticle dispersion.
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